CN102701182B - Blending pyrolysis method for preparing catalytic carbon film - Google Patents
Blending pyrolysis method for preparing catalytic carbon film Download PDFInfo
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Abstract
The invention belongs to the field of reaction and separation in the chemical engineering subject, in particular to a preparation method for a carbon film material with catalytic action. The preparation method is characterized in that: a catalyst is introduced into a carbon film matrix through a step for pretreating a carbon-containing precursor, a step for dispersing and embedding the catalyst and a step for blending and pyrolyzing, so that a porous catalytic carbon film with dual functions of catalyzing and separating is prepared. When reaction materials flow from one side of the catalytic carbon film to the other side through a porous channel, the aim of finishing a chemical reaction process inside the catalytic carbon film is fulfilled. The invention has the beneficial effects: a novel film material preparation method which contributes to synchronous performance of a micro-scale chemical reaction and substance separation and increase in the conversion rate, yield and selectivity of the reaction is provided, the product production process is shortened, and the costs of equipment and a product are lowered.
Description
Technical field
The invention belongs to the reaction in Chemical waste-water and separation field, especially relate to one kind and there is catalytic action
Carbon membrane material preparation method.
Background technology
Carbon membrane is a kind of novel porous inorganic separating film, have efficiently, energy-conservation, easy to operate, heat-resisting, corrosion-resistant, use
The advantages of life-span length and separating property are high, all shows tempting application prospect in numerous areas, such as hydrogen recovery, synthesis gas
（H2/CO）Proportion adjustment, acid gas removal（CO2/ hydrocarbon and H2S/ hydrocarbon）, gas dehydration, helium recovery（He/N2）, at sewage
Reason, Separation of Proteins and film reaction process etc.（A.F. Ismail, L.I.B. David. Journal of Membrane
Science, 193(2001): 1-18；C. Song, T. Wang, Y. Pan, J. Qiu. Separation and
Purification Technology, 51(2006): 80-84；T.N. Shah, H.C. Foley, A.L. Zydney.
Journal of Membrane Science, 295(2007): 40-49.）.More and more researcheres are attracted in recent years
Attract attention, it has also become the study hotspot of the crossing domain such as Chemical waste-water and membrane separation technique.Carbon membrane is typically in inertia or true
Under air atmosphere, it is prepared from through pyrolysis carbon containing precursor.The separating property of carbon membrane significantly be subject to carbon containing precursor, pyrolytical condition and
The impact of the factors such as film-forming method.In recent years, researcher develops multiple methods improving Gas Separation Properties of Carbon Menbrane, such as to masking
Volatile small molecule or labile Organic substance is introduced in carbon containing precursor used（Tin PS, Chung T-S, Hill
AJ. Ind. Eng. Chem. Res., 43(2004): 6476-6483.）, side chain, functional group（Yoshimune M,
Fujiwara I, Haraya K. Carbon, 45(2007): 553-560.）, zeolite（Wang Tonghua, Liu Qingling, Qiu Jie
Mountain. Chinese invention patent, ZL200510200871.9）, metallic salt（Park HB, Jung CH, Kim YK, Lee
YM. J. Membr. Sci., 235(2004): 87–98.）Deng.Carbon membrane can also be used for the Separation ＆ Purification of liquid mixture.
Bauer et al.（Bauer JM, Elyassini J, Moncorge G. Key Engineering Materials, 1991:
207-212.）Carbon membrane is used for drink water purifying and chemical wastewater treatment；Shah et al.（T.N. Shah, H.C. Foley,
A.L. Zydney. Journal of Membrane Science, 295(2007): 40-49.）Efficiently separated with carbon membrane
Protein.In addition, playing carbon membrane heat-resisting quantity, chemical inertness and separation property for comprehensive, can inert carbon membrane encapsulation film forming anti-
Answer device, improve chemical reaction, expand and there is the application of value segment（Zhang Bing, Wu Yonghong, Fu Chengbi, Xu Tiejun.
Chinese invention patent, 201010118376）.
Although through decades development, carbon membrane research is not achieved with many notable achievements, still in laboratory stage, real
Existing commercial Application.The bottleneck problem limiting its development is the failure to give full play to carbon membrane overall merit.The opening of inertia carbon membrane reactor
Sending out application undoubtedly provides a practical way for its development, but to fundamentally improve carbon membrane cost performance and the market competitiveness,
Its overall merit must be given full play to further, be applied to higher level process and field, particularly exploitation has specific function
Carbon membrane.Through further investigation, the present inventor finds that preparation has the catalysis carbon membrane of catalytic reaction function in strengthening chemical reaction process
When, serve the effect of similar microreactor, can comprehensively play the features such as its corrosion resistance, separation property, porous, be directed to
Property ground improve reaction conversion ratio and selectivity, thus increasing substantially carbon membrane cost performance.Therefore, research and development are catalyzed carbon membrane
Preparation method and technique will greatly promote development and the industrial applications of carbon membrane.
Content of the invention
Goal of the invention：It is an object of the invention to provide a kind of preparation method of catalysis carbon membrane.Specifically, using blending heat
Catalyst dispersion is embedded in carbon containing precursor solution, prepares through pyrolytic process and has catalytic concurrently, and separation property is thermally-stabilised
Property and chemical stability porous catalytic carbon membrane, can be used for completing chemical reaction process, be carbon membrane improve the market competitiveness, promote
Industrial applications provide foundation early.
Technical scheme：
A kind of prepare catalysis carbon membrane blending pyrolysismethod it is characterised in that：It is to be divided with carbon containing precursor pretreatment, catalyst
Dissipate to embed and constitute with blending three steps of pyrolysis, the prepared catalysis carbon membrane having catalysis and separation function concurrently, can be used for chemical reaction
Process, its step is as follows：
（1）Carbon containing precursor pretreatment：Carbon containing precursor includes solid-state or liquid, solid carbon-contg precursor be powder or
Mud paste, preprocess method be pulverize, stirring or one or more of preforming；Liquid carbon containing precursor is solution or suspension
Liquid, preprocess method be solvent dilution, ultrasound wave dispersion, standing or stirring one or more of；
（2）Catalyst dispersion is embedded：By catalyst through one of mechanical agitation, ultrasound wave dispersion, preforming or masking
Or several method dispersion is embedded in pretreated carbon containing precursor, catalyst accounts for the 0.5- of carbon containing precursor mass content
50%, obtain the solid mixture that catalyst is constituted with carbon containing precursor after drying；
（3）Blending pyrolysis：The solid mixture obtaining is pyrolyzed at high temperature, pyrolysis atmosphere is noble gases or vacuum,
Temperature is 500～1000 DEG C, and heating rate is 0.2 DEG C～20 DEG C/min, and inert gas flow velocity is 10～300mL/min, constant temperature
Time is 1-5 hour；Just carbon membrane must be catalyzed after cooling.
The carbon containing precursor being adopted is polyimides, poly furfuryl alcohol, phenolic resin, polyether sulfone, polyvinylidene chloride, fiber
One or more of element or coal, existence is solid-state or liquid.
The species of catalyst is the copper of powder or solution state, nickel, aluminum, platinum, zinc, chromium, silver, ferrum, copper oxide, oxidation
One or more of nickel, aluminium oxide, platinum oxide, zinc oxide, ferrum oxide, chromium oxide or silver oxide.
In step（2）Masking is carbon containing precursor by being mixed with catalyst in pottery, rustless steel, carbonaceous or phenolic resin
A kind of supporter on film forming, film build method is one of solvent evaporated method, infusion process or spread coating.
Be catalyzed carbon membrane is shaped as tabular or tubulose.
The invention has the beneficial effects as follows：
Using such scheme it is achieved that catalyst is embedded in carbon membrane porous channel, obtain that there is catalysis and separation of double
The carbon membrane of function；The comprehensive advantage of carbon membrane can be given full play to by being catalyzed the preparation and application of carbon membrane, be carbon membrane functionalization and
It lays the foundation in the application of the value segments such as chemical reaction, also fundamentally improves the cost performance of carbon membrane simultaneously.Cause
This, the popularization and application of catalysis carbon membrane will promote development and the industrial applications of new membrane separation technique.
Brief description：
Fig. 1 is catalyzed the stereoscan photograph of carbon membrane for phenolic resin base；
Fig. 2 is the stereoscan photograph of polyimide-based catalysis carbon membrane；
Fig. 3 is the stereoscan photograph of polyethers sulfuryl catalytic carbon film；
Fig. 4 is catalyzed the stereoscan photograph of carbon membrane for cellulose base；
Fig. 5 is catalyzed the stereoscan photograph of carbon membrane for poly furfuryl alcohol base.
Embodiment：Describe highly preferred embodiment of the present invention below in conjunction with technical scheme and accompanying drawing in detail.
It is solid-state or liquid according to carbon containing precursor existence, be respectively adopted specific embodiment 1 or specific embodiment party
Formula 2 preparation catalysis carbon membrane.
Specific embodiment 1：
First, by solid carbon-contg precursor in grinder with 300 ~ 1500 revs/min of rotating speed agitation grinding 0 ~ 48 hour,
It is 0.5 ~ 50 micron-sized powder to mean diameter.Again powder or solution shape catalyst are passed through mechanical agitation or blending method
Dispersed entrance carbon containing precursor powder, i.e. polyimides or polyether sulfone or phenolic resin or polyvinylidene chloride or cellulose
Or one or more of poly furfuryl alcohol or coal；To the catalyst/carbon containing precursor mixed-powder of above-mentioned formation, add solvent and add
Plus agent, make catalyst account for the 0.5%～50% of gross mass content.Uniform mud paste carbon containing is made by mechanical agitation or blending method
Precursor mixture；Through room temperature ageing a period of time, tabular or tubulose are compressed on forming machine, then evaporate through solvent, do
After dry, obtain carbon containing precursor film.The above-mentioned carbon containing precursor film made is pyrolyzed；Pyrolytical condition is vacuum environment or inertia
Under a kind of protection in gas such as nitrogen or argon or helium, heating rate is 0.2 DEG C～20 DEG C/min, and pyrolysis final temperature is 500
DEG C～1000 DEG C, inert gas flow velocity is 10～300mL/min, and constant temperature 1-5 hour.After being down to room temperature, just obtain catalytic carbon
Film.
Specific embodiment 2：
First, add solvent in liquid carbon containing precursor, through power be 30 ~ 100 watts of ultrasonic assistant disperse 0 ~ 2 hour,
Standing stirs 0 ~ 12 hour, obtains solution or suspension after the dilution that mass concentration is 5 ~ 20% for 0 ~ 24 hour, 300 ~ 1500 revs/min
Liquid.Again by powder or solution shape catalyst adopt mechanical agitation or one of ultrasonic assistant or sol-gel process or
Several, it is distributed to carbon containing precursor solution or suspension, i.e. polyimides or polyether sulfone or phenolic resin or polyvinylidene chloride
Or one or more of cellulose or poly furfuryl alcohol；Catalyst and carbon containing precursor solution mass ratio is made to control 0.5%～50%；
Mass content controls 0.5%～50% carbon containing precursor in the solution.The solution of above-mentioned formation is adopted solvent evaporated method or leaching
Stain method or spread coating masking, obtain tabular or tubular film, or make heterogeneous body film on supporter.Wherein, supporter material
For pottery or rustless steel or one of carbonaceous or phenolic resin.Prepare carbon containing precursor film through solvent evaporation, drying.Will
Directly pyrolysis or first crosslinked solidification are pyrolyzed or are first pyrolyzed through air pre-oxidation again the above-mentioned carbon containing precursor film made again；Pyrolysis
Atmosphere is that under vacuum environment or noble gases such as nitrogen or the protection of one of argon or helium, heating rate is 0.2 DEG C～20
DEG C/min, it is pyrolyzed final temperature and is 500 DEG C～1000 DEG C, inert gas flow velocity is 10～300mL/min, and constant temperature 1-5 hour.It is down to
After room temperature, just obtain being catalyzed carbon membrane.
Embodiment 1
By Powdered phenolic resins with 300 revs/min of mechanical agitation 5 hours, it is 50 micron-sized powder to mean diameter.
Take Phenolic resin powder 30g and hexamethylenetetramine 3.6g, stirring mixes rear 150 DEG C of constant temperature 1 hour, precuring.Stir after cooling
Mix and be ground to brick-red powder.Add suitable quantity of water, Cu/ZnO/Al2O3Catalyst and 3.6g additive fiber element stir evenly, and become
Mud paste, is aged 80 minutes.Again above-mentioned preforming carbon containing precursor is pressed into tabular on forming machine, spontaneously dries 48 little
When.Put into retort, nitrogen flow is 70mL/min, with the speed of 2 DEG C/min from room temperature to 400 DEG C, then with 1 DEG C/min
It is warmed up to 600 DEG C, after 600 DEG C of constant temperature 1 hour, Temperature fall.Obtain being catalyzed carbon membrane.Fig. 1 show prepared by this embodiment
Catalysis carbon membrane stereoscan photograph.In 190 DEG C of reaction temperature, H2O/CH3When OH raw materials components mole ratio is 1, reaction mass is made to flow through
The microcellular structure of catalysis carbon membrane, completes chemical reaction.The conversion ratio to methanol in methanol steam reforming reaction for this catalysis carbon membrane
For 98.5%.
Embodiment 2
Block phenolic resin is passed through ball mill attrition grinding 12 hours, and with 1500 revs/min of mechanical agitation 1 hour,
It is 32 micron-sized powder to mean diameter.Take Phenolic resin powder 30g and hexamethylenetetramine 3.6g, 150 after stirring mixing
DEG C constant temperature 1 hour, precuring.After cooling, agitation grinding is to brick-red powder.Add water, Cu/ZnO/Al2O3Catalyst and
3.6g additive fiber element stirs evenly, and becomes mud paste, is aged 80 minutes.Above-mentioned preforming carbon containing precursor is suppressed on forming machine
Become tabular, spontaneously dry 36 hours.Soaked and stagnant joined in 7g phenolic resin, 1.2g hexamethylenetetramine and 11.8g ethanol
In the solution becoming, take out after 5 seconds, spontaneously dry.Put into retort, nitrogen flow 200mL/min, with the speed of 5 DEG C/min from
Room temperature rises to 700 DEG C, and in 700 DEG C of constant temperature 1 hour, Temperature fall, obtains being catalyzed carbon membrane.In 220 DEG C of reaction temperature, H2O/
CH3When OH raw materials components mole ratio is 1, the microcellular structure that reaction mass flows through catalytic carbon film is made to complete chemical reaction.This is catalyzed carbon membrane
Conversion ratio to methanol in methanol steam reforming reaction is 99.3%.
Embodiment 3
Average particle diameter is taken to be 22 micron-sized Phenolic resin powder 30g and hexamethylenetetramine 3.6g, 150 after stirring mixing
DEG C constant temperature 1 hour, precuring.After cooling, agitation grinding is to brick-red powder.Add suitable quantity of water and 3.6g（12%）Additive
Cellulose stirs evenly, and becomes mud paste, is aged 80 minutes.Above-mentioned preforming carbon containing precursor is pressed into tubulose on forming machine, from
So it is dried 36 hours, obtain phenolic resin supporter.With 7g phenolic resin, 1.2g hexamethylenetetramine, 11.8g ethanol, and Cu/
ZnO/Al2O3Catalyst is made into film making solution jointly.Supporter be impregnated in and take out after 5 seconds in preparation liquid, spontaneously dry.Put into
Retort, helium gas flow is 70mL/min, with the speed of 2 DEG C/min from room temperature to 850 DEG C, and constant temperature 2 hours, fall naturally
Temperature, obtains being catalyzed carbon membrane.In 220 DEG C of reaction temperature, H2O/CH3When OH raw materials components mole ratio is 1, reaction mass is made to flow through catalytic carbon
The microcellular structure of film completes chemical reaction.This catalysis carbon membrane is 99.5% to the conversion ratio of methanol in methanol steam reforming reaction.
Embodiment 4
Block phenolic resin is passed through ball mill attrition grinding 48 hours, and with 500 revs/min of mechanical agitation 10 hours,
It is 0.5 micron-sized powder to mean diameter.Take Phenolic resin powder 30g and hexamethylenetetramine 3.6g, 150 after stirring mixing
DEG C constant temperature 1 hour, precuring.After cooling, agitation grinding is to brick-red powder.Add the Pt/Al of water, 0.5%wt2O3Powder
Shape catalyst and 3.6g additive fiber element stir evenly, and become mud paste, ageing.By above-mentioned preforming carbon containing precursor on forming machine
It is pressed into tubulose, spontaneously dry 24 hours.It is made into 8% film making solution of N-methyl ketopyrrolidine with polyimides, supporter is soaked
Stain is taken out after 5 seconds in the preparation liquid, and shady place is dried.Put into retort, nitrogen flow 50mL/min, with the speed of 2 DEG C/min
From room temperature to 600 DEG C, and constant temperature 1 hour, Temperature fall, obtain being catalyzed carbon membrane.Fig. 2 show prepared by this embodiment
Catalysis carbon membrane stereoscan photograph.In 220 DEG C of reaction temperature, feed flow rate 6.5 mg/min-1When, make reaction mass flow through catalysis
The microcellular structure of carbon membrane completes chemical reaction.This catalysis carbon membrane reaches 78% to cyclohexane dehydrogenation benzene reaction cyclohexane conversion ratio.
Embodiment 5
Block phenolic resin is passed through ball mill attrition grinding 40 hours, and with 800 revs/min of mechanical agitation 6 hours, extremely
Mean diameter is 15 micron-sized powder.Take Phenolic resin powder 30g and hexamethylenetetramine 3.6g, latter 150 DEG C of stirring mixing
Constant temperature 1 hour, precuring.After cooling, agitation grinding is to brick-red powder.Add water, Cr2O3/Al2O3Powder catalyst
And 3.6g additive fiber element stirs evenly, become mud paste, be aged 80 minutes.Above-mentioned preforming carbon containing precursor is pressed on forming machine
Make tabular, spontaneously dry 48 hours.With the nitrogen nitrogen dimethyl acetylamide 10% of polyether sulfone as film making solution, supporter is soaked
Stain is taken out after 15 seconds in the preparation liquid, spontaneously dries.Put into retort, argon flow amount 70mL/min, with the speed of 2 DEG C/min from
Room temperature is raised to 600 DEG C, in 600 DEG C of constant temperature 5 hours, Temperature fall, obtains being catalyzed carbon membrane.Fig. 3 show prepared by this embodiment
Catalysis carbon membrane stereoscan photograph.In 550 DEG C of reaction temperature, feed flow rate 0.03 mg/min-1When, so that reaction mass is flowed through
The microcellular structure of catalysis carbon membrane completes chemical reaction.In this catalysis carbon membrane centering preparing isobutene through dehydrogenation of iso-butane reaction, iso-butane turns
Rate reaches 53.2%.
Embodiment 6
Lumped coal is passed through ball mill attrition grinding 40 hours, and with 1200 revs/min of mechanical agitation 12 hours, to average
Particle diameter is 35 micron-sized powder.Take coal dust end 30g, add water, Cr2O3/Al2O3Powder catalyst and 5g contain 15% polyamides
Imide liquor, stirs evenly into mud paste, is aged 120 minutes.Above-mentioned preforming carbon containing precursor is pressed into flat board on forming machine
Shape, spontaneously dries 48 hours.With the nitrogen nitrogen dimethyl acetylamide 10% of polyether sulfone as film making solution, supporter be impregnated in masking
Take out after 10 seconds in liquid, spontaneously dry 24 hours.Put into retort, argon flow amount 100mL/min, with the speed of 2 DEG C/min from
Room temperature is raised to 600 DEG C, in 600 DEG C of constant temperature 5 hours, Temperature fall, obtains being catalyzed carbon membrane.In 550 DEG C of reaction temperature, feed flow rate
0.03 mg/min-1When, make the microcellular structure that reaction mass flows through catalytic carbon film complete chemical reaction.This catalysis carbon membrane centering is different
In the reaction of butane dehydrogenation preparing isobutene, iso-butane conversion ratio reaches 55.2%.
Embodiment 7
With porous graphite flat board as supporter, will contain 15% polyimides N-methyl ketopyrrolidine be solvent with 300 turns/
Point stirring is diluted to 8% for 12 hours, and with 100 watts of power ultrasonic aid dispersion 0.25 hour, standing 24 hours.Take polyamides sub-
Amine aqueous solution and 15% ferrum-based catalyst are mixed into film making solution, supporter be impregnated in and take out after 5 seconds in preparation liquid, surface is brushed again
Apply a preparation liquid, spontaneously dry 24 hours.Put in retort, nitrogen flow 70mL/min, with the speed of 2 DEG C/min from room
Temperature is warmed up to 400 DEG C, then is warmed up to 600 DEG C with 1 DEG C/min, in 600 DEG C of constant temperature 1 hour, Temperature fall, obtains being catalyzed carbon membrane.
Fig. 4 show the cellulose base catalysis carbon membrane stereoscan photograph prepared by this embodiment.In 390 DEG C of reaction temperature, H2O/CO
When raw materials components mole ratio is 1, the microcellular structure that reaction mass flows through catalytic carbon film is made to complete chemical reaction.This catalysis carbon membrane is to water coal
The conversion ratio of gas transformationreation is 88.8%.
Embodiment 8
With porous charcoal flat board as supporter, will contain 20% cellulose N-methyl ketopyrrolidine is that solvent is stirred with 1500 revs/min
Mix 1 hour and be diluted to 10%, and with 30 watts of power ultrasonic aid dispersion 2 hours, stand 1 hour.Take polyimide solution with
12% ferrum-based catalyst is mixed into film making solution, supporter be impregnated in and take out after 25 seconds in preparation liquid, spontaneously dry 24 hours.
Put into retort, nitrogen flow 70mL/min, be raised to 400 DEG C with the speed of 2 DEG C/min from room temperature, then be warmed up to 1 DEG C/min
600 DEG C, constant temperature 1 hour, Temperature fall, obtain being catalyzed carbon membrane.In 390 DEG C of reaction temperature, H2When O/CO raw materials components mole ratio is 1,
The microcellular structure that reaction mass flows through catalytic carbon film is made to complete chemical reaction.This is catalyzed the conversion to water gas shift reaction for the carbon membrane
Rate is 86.5%.
Embodiment 9
With porous ceramicss flat board as supporter, the acetone soln containing 10% poly furfuryl alcohol and 20% ferrum-based catalyst is that masking is molten
Liquid, brushes in supporting external surface, spontaneously dries 24 hours.Put into retort, nitrogen flow 70mL/min, with 2 DEG C/min's
Speed is raised to 800 DEG C from room temperature, in 800 DEG C of constant temperature 1 hour, Temperature fall.Obtain being catalyzed carbon membrane.Fig. 5 show this embodiment
Prepared catalysis carbon membrane stereoscan photograph.In 390 DEG C of reaction temperature, H2O/CO raw materials components mole ratio is 2:When 1, make reactant
The microcellular structure through being catalyzed carbon membrane for the stream completes chemical reaction.This is catalyzed carbon membrane
91.2%.
Embodiment 10
Pt/Al with porous stainless steel flat board as supporter, containing 5% polyvinylidene chloride and 0.5%wt2O3Powder is masking
Solution, supporter be impregnated in and takes out after 5 seconds in preparation liquid, spontaneously dry.Put into retort, under vacuum, with 2 DEG C/min
Speed be raised to 800 DEG C from room temperature, in 800 DEG C of constant temperature 1 hour, Temperature fall, obtain being catalyzed carbon membrane.In 200 DEG C of reaction temperature,
Feed flow rate 6.5 mg/min-1When, make the microcellular structure that reaction mass flows through catalytic carbon film complete chemical reaction.This is catalyzed carbon membrane
64% is reached to cyclohexane dehydrogenation benzene reaction cyclohexane conversion ratio.
By solid-state or liquid carbon containing precursor after pretreatment, mix with catalyst needed for certain chemical reaction, then this is mixed
Compound makes lamellar or tubular film, obtains after pyrolysis being catalyzed carbon membrane.Wear when chemical reaction material flows through from catalysis carbon membrane side
When crossing to opposite side, that is, complete chemical reaction process.
Claims (1)
1. a kind of prepare catalysis carbon membrane blending pyrolysismethod it is characterised in that：
By Powdered phenolic resins with 300 revs/min of mechanical agitation 5 hours, it is 50 micron-sized powder to mean diameter；Take phenol
Urea formaldehyde powder 30g and hexamethylenetetramine 3.6g, stirring mixes rear 150 DEG C of constant temperature 1 hour, precuring；After cooling, stirring is ground
It is milled to brick-red powder；Add suitable quantity of water, Cu/ZnO/Al2O3Catalyst and 3.6g additive fiber element stir evenly, and become mud cream
Shape, is aged 80 minutes；Again above-mentioned preforming carbon containing precursor is pressed into tabular on forming machine, spontaneously dries 48 hours；
Put into retort, nitrogen flow is 70mL/min, with the speed of 2 DEG C/min from room temperature to 400 DEG C, then with 1 DEG C/min liter
To 600 DEG C, after 600 DEG C of constant temperature 1 hour, Temperature fall obtains being catalyzed carbon membrane temperature；In 190 DEG C of reaction temperature, H2O/CH3OH enters
When material mol ratio is 1, makes reaction mass flow through the microcellular structure of catalytic carbon film, complete chemical reaction；This catalysis carbon membrane is to methanol
In steam reforming reaction, the conversion ratio of methanol is 98.5%.
2. a kind of prepare catalysis carbon membrane blending pyrolysismethod it is characterised in that：
Block phenolic resin is passed through ball mill attrition grinding 12 hours, and with 1500 revs/min of mechanical agitation 1 hour, to flat
All particle diameter is 32 micron-sized powder；Take Phenolic resin powder 30g and hexamethylenetetramine 3.6g, stirring mixes rear 150 DEG C of perseverances
Temperature 1 hour, precuring；After cooling, agitation grinding is to brick-red powder；Add water, Cu/ZnO/Al2O3Catalyst and 3.6g add
Plus agent cellulose stirs evenly, become mud paste, be aged 80 minutes；Above-mentioned preforming carbon containing precursor is pressed into flat board on forming machine
Shape, natural drying 36 hours；Be impregnated in that 7g phenolic resin, 1.2g hexamethylenetetramine and 11.8g ethanol is made into is molten
In liquid, take out after 5 seconds, spontaneously dry；Put into retort, nitrogen flow 200mL/min, with the speed of 5 DEG C/min from room temperature liter
To 700 DEG C, and in 700 DEG C of constant temperature 1 hour, Temperature fall, obtain being catalyzed carbon membrane；In 220 DEG C of reaction temperature, H2O/CH3OH feeds
When mol ratio is 1, the microcellular structure that reaction mass flows through catalytic carbon film is made to complete chemical reaction；This catalysis carbon membrane steams to methanol-water
In gas reforming reaction, the conversion ratio of methanol is 99.3%.
3. a kind of prepare catalysis carbon membrane blending pyrolysismethod it is characterised in that：
Average particle diameter is taken to be 22 micron-sized Phenolic resin powder 30g and hexamethylenetetramine 3.6g, stirring mixes rear 150 DEG C of perseverances
Temperature 1 hour, precuring；After cooling, agitation grinding is to brick-red powder；Add suitable quantity of water and 3.6g additive fiber element stirs
Even, become mud paste, be aged 80 minutes；Above-mentioned preforming carbon containing precursor is pressed into tubulose on forming machine, spontaneously dries 36
Hour, obtain phenolic resin supporter；With 7g phenolic resin, 1.2g hexamethylenetetramine, 11.8g ethanol and Cu/ZnO/Al2O3
Catalyst is made into film making solution jointly；Supporter be impregnated in and take out after 5 seconds in preparation liquid, spontaneously dry；Put into retort, helium
Throughput is 70mL/min, with the speed of 2 DEG C/min from room temperature to 850 DEG C, and constant temperature 2 hours, Temperature fall, urged
Change carbon membrane；In 220 DEG C of reaction temperature, H2O/CH3When OH raw materials components mole ratio is 1, reaction mass is made to flow through the micropore knot of catalytic carbon film
Structure completes chemical reaction；This catalysis carbon membrane is 99.5% to the conversion ratio of methanol in methanol steam reforming reaction.
4. a kind of prepare catalysis carbon membrane blending pyrolysismethod it is characterised in that：
Block phenolic resin is passed through ball mill attrition grinding 48 hours, and with 500 revs/min of mechanical agitation 10 hours, to flat
All particle diameter is 0.5 micron-sized powder；Take Phenolic resin powder 30g and hexamethylenetetramine 3.6g, stirring mixes rear 150 DEG C of perseverances
Temperature 1 hour, precuring；After cooling, agitation grinding is to brick-red powder；Add the Pt/Al of water, 0.5%wt2O3Powder is urged
Agent and 3.6g additive fiber element stir evenly, and become mud paste, ageing；Above-mentioned preforming carbon containing precursor is suppressed on forming machine
Become tubulose, spontaneously dry 24 hours；It is made into 8% film making solution of N-methyl ketopyrrolidine with polyimides, supporter be impregnated in
Take out after 5 seconds in preparation liquid, shady place is dried；Put into retort, nitrogen flow 50mL/min, with the speed of 2 DEG C/min from room
Temperature is warmed up to 600 DEG C, and constant temperature 1 hour, Temperature fall, obtains being catalyzed carbon membrane；In 220 DEG C of reaction temperature, feed flow rate 6.5
mg/min-1When, make the microcellular structure that reaction mass flows through catalytic carbon film complete chemical reaction；This catalysis carbon membrane is to cyclohexane dehydrogenation
Benzene reaction cyclohexane conversion ratio processed reaches 78%.
5. a kind of prepare catalysis carbon membrane blending pyrolysismethod it is characterised in that：
Block phenolic resin is passed through ball mill attrition grinding 40 hours, and with 800 revs/min of mechanical agitation 6 hours, to average
Particle diameter is 15 micron-sized powder；Take Phenolic resin powder 30g and hexamethylenetetramine 3.6g, stirring mixes rear 150 DEG C of constant temperature 1
Hour, precuring；After cooling, agitation grinding is to brick-red powder；Add water, Cr2O3/Al2O3Powder catalyst and
3.6g additive fiber element stirs evenly, and becomes mud paste, is aged 80 minutes；Above-mentioned preforming carbon containing precursor is suppressed on forming machine
Become tabular, spontaneously dry 48 hours；With the nitrogen nitrogen dimethyl acetylamide 10% of polyether sulfone as film making solution, supporter is impregnated
Take out after 15 seconds in the preparation liquid, spontaneously dry；Put into retort, argon flow amount 70mL/min, with the speed of 2 DEG C/min from room
Temperature rise to 600 DEG C, in 600 DEG C of constant temperature 5 hours, Temperature fall, obtains being catalyzed carbon membrane；In 550 DEG C of reaction temperature, feed flow rate
0.03 mg/min-1When, make the microcellular structure that reaction mass flows through catalytic carbon film complete chemical reaction；This catalysis carbon membrane centering is different
In the reaction of butane dehydrogenation preparing isobutene, iso-butane conversion ratio reaches 53.2%.
6. a kind of prepare catalysis carbon membrane blending pyrolysismethod it is characterised in that：
Lumped coal is passed through ball mill attrition grinding 40 hours, and with 1200 revs/min of mechanical agitation 12 hours, to mean diameter
For 35 micron-sized powder；Take coal dust end 30g, add water, Cr2O3/Al2O3Powder catalyst and 5g contain 15% polyimides
Solution, stirs evenly into mud paste, is aged 120 minutes；Above-mentioned preforming carbon containing precursor is pressed into tabular on forming machine, from
So it is dried 48 hours；With the nitrogen nitrogen dimethyl acetylamide 10% of polyether sulfone as film making solution, supporter be impregnated in 10 in preparation liquid
Take out after second, spontaneously dry 24 hours；Put into retort, argon flow amount 100mL/min, with the speed of 2 DEG C/min from room temperature liter
To 600 DEG C, in 600 DEG C of constant temperature 5 hours, Temperature fall, obtain being catalyzed carbon membrane；In 550 DEG C of reaction temperature, feed flow rate 0.03
mg/min-1When, make the microcellular structure that reaction mass flows through catalytic carbon film complete chemical reaction；This catalysis carbon membrane centering iso-butane takes off
In the reaction of hydrogen preparing isobutene, iso-butane conversion ratio reaches 55.2%.
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